Heterocyclic monoazodyestuffs



Patented Nov. 10, 1953 HETEROCYCLIC MONOAZ OD YESTUFFS Ernst Fischer, Oflenbach (Main), Germany, as-

signor to Farbwerke Hoechst A. G., vormals Meister Lucius und Briining, Frankfurtam Main Hochst, Germany, a company of Germany No Drawing. Application July 28 1951,

' Serial No. 239,177

Claims priority, application Germany August 3, 1950 vClaims. (01. 260-164) 1 The present invention relates to waterinsoluble monoazodyestufis to be used as pigments.

More particularly, this invention relates to monoazodyestufis of the general formula N 1% OH {7/ Z1 oonnn zi 18 l. in which X indicates a substituent of the group consisting of alkyl, alkoxy and halogen; Y indicates a radical of the group consisting of carbazol, diphenylenoxide and diphenylensulfide wherein the hydroxy group and the azo group are in ortho-position to each other; R indicates an aryl radical of the group consisting of phenyl and naphthyl; Z1, Z2 and Z3 each indicates a member of the group consisting of H, alkyl, alkoxy; halogen.

This invention especially relates to monoazodyestufis of the general formula *in which X indicates a substituent of the group consisting of alkyl, alkoxy and halogen; R indicates an aryl radical of the group consisting of phenyl and naphthyl; Z1, Z2 and Z3 each indicates a member of the group consisting of H, alkyl, alkoxy and halogen.

I have found that the aforesaid dyestuffs can be manufactured by coupling a diazo compound of an amine of the general formula wherein X indicates a substituent of the group I oxydiphenylenesulfide-Z-carboxylic consisting of alkyl, alkoxy and halogen, with an arylide of 2-oxycarbazol-3-carboxylic acid, 3- oxydiphenyleneoxide-2rcarboxylic acid or 3- acid, the compounds being soselected that they contain no water-solubilising groups, for example sulphonic acid or carboxylic acid groups.

It has been found that the water-insoluble monoazodyestuifs obtained according to my invention are especially suitable for the dyeing of plastic masses from high molecular organic compounds and for the manufacture of color lakes in the usual manner of mixing a pigment with carrier material or by efiecting the coupling of the dyestufi' components in the presence of a suitable carrier material for color lake production.

Besides the afore-mentioned objects, the present invention comprises plastic masses from high molecular organic compounds dyed with the afore-said dyestuffs, and color lakes prepared from such dyestufis or by producing such dyestuffs in the presence of a suitable carrier materialr V The new dyestufls produced according to my invention yield brown, brown violet or blue grey color shades of good fastness properties.

They are suitable especially for the dyeing of plastic masses from high molecular organic compounds, for example condensation products from formaldehyde and urea, phenol or amines, vinyl compounds, rubber and so on and they can in addition find application with advantage for the manufacture of color lakes which are fast to oil and light, and also, by adding them to the spinning solutions, for the production of spun-dyed acetate artificial silk and viscose artificial silk.

The dyestuffs obtained according to the present process have the advantage over the known dyestuffs described in German patent specification No. 741,357, for the manufacture of which the samelazo ,components are employed that they do not "bleed "out into undyed polymerisation products from vinyl chloride.

The following examples serve to illustrate the invention, but they are not intended to limitgit thereto.

Example 1 15.9 parts by weight of l -arnino-gmethqxybenzene-S-carboxylic acid-4-phenyl anilideare diazotised in the customary manner. flhereupon, for removal of the excess of mineral acid; the suspension of the diazo compound is treatedwith sodium acetate and then, with very good stirring,

a solution of 16.9 parts by weight of l-(2"-hydroxycarbazole-3-carboylamino)-4 chlorobenzene in dilute caustic soda solution is caused to lq f emphasi mrleiesl :Py-sraduel maths- .9 5'

. 011, h u ee be s r Pm- I um a Pie-We Peu he estimati erti e fl ei e ms i e li9i ..j is, tm Y??? $1 .9 a ia se 12. w? a'sfollows'." i 100 parts by weight ofapolymerisationtproduct irom vinyl chloride, 50 parts by weight of phthalic .acid dibutyl .ester.(n),:31vhich .actsas plasticisingagent; 0.2 parltby weight of titanium dioxide and 0.3.par't'by weight'of. the azo+dyiestufi e aml l ee m e isei 9 alseeaies :59. 1 a; 1%)???- Tile s Sbtaine'da mass 'of a 'sn'riilar consistency to soft upbe apd o redd hliqwp 92 9M. .weiebis s not bleed. outinto d polymerisation product pith; 91 th r nati nal pis emic before kneading."

ployedi fd" The'grey dyestufi produced is filtered off, well formula:

-c ONHO & O

NH OH 01 6 z 1 CON-H- Example 2 15.9 parts by weight of l-amino-Z-methoxybenzene- 5'-carboxylic acid-4-phenyl anilide are 'gliazotised the gcustomary manner. Into the ofrth edi azo compound which has been neutralised'to'Con'go red with sodium acetate, is stirred aqsolutiongof 18.2 parts by weight of 1-(3'- -'hydroxydiphenylene oxide 2 carboylamino) 2: 5-. iim ethg gybenzene in dilute caustic soda soiofi andthewhole is then heated to 40-5o c.

washedland dried. It possesses the formula:

0 ONE It can be employed in the iollowing manner for the dyeing of rubber:

A mixture of rubber, filling materials, sulphur,

vulcanisation accelerator and-2 per cent; of the The dyestuft obtained by the method described in Example 1 from 15.9 parts-by weight of 1- amino 2-methoxybenzene-5-carboxylic acid-4'- phenylanilide and 17.5 parts by weight of l-(3- hydroxydiphenylene sulphide 2' carboxylamino)-2-methoxybenzene forms a grey violet powder by means of which, using the process also described in that example, polymerisation products from vinyl chloride can be dyed in grey blue shades fast to light. Thedyeings donut bleed 15 ou into undyed pglymerisation product The dyestufi here employed possesses'the structural formula:

ooNn

CHaO

com:

OH: Example 4 From the diazo compound of 15.9 parts by weight of 1-amino-2-methoxybenzene carboxylic acid-4'-phenyl anilide and 17.6 parts by weight of 2-(2'-hydroxycarbazole-3'-carboylamino) -naphtha1ene, by the method described in Examples 1 and 2, a brown dyestuff is obtained. It has the formula:

CONH

CHaO

OONH

The lakes produced with this dyestuff yield violettish-brown shades of good fastness to oil and light.

The coupling can also be carried out in the presence of a suitable carrier material for color lake production.

Example 5 By employing in Example 1 instead of 16.9 parts by weight of 1-(2'-hydroxycarbazole-3'- oarboylamino)-4-chlorobenzene 15.1 parts by 'weight of 1 (2' hydroxycarbazole-3'-carboylamino) -benzene, there is obtained a dyestuff of similar color shade. It possesses the structural formula:

0 ONE- N II N c ONHCQH;

the monoazo dyestufis which are produced and which likewise possess good fastness properties:

Diazo component ,Azo component Color shade l-amino-z-methoxy- 1-(2'41ydroxycarba- Brown.

benzene-Marboxylic zole-3-carboylamiacid-4'-phenyl anilno) -4-methylbenide. zene.

Do 1-(2-hydrcxycarba- Reddish brown.

zole-3-carboylamino)-4-bromobenzene.

1-amino-2-chloroben- 1-(2'-hydroxycarba- Yellowish brown.

zene-5-carboxylic zole-3-carboylemiacid-4-phenyl- -no)-4-chlorobenzene. anilide. l-amino-Z-bromoben- -...-d0 Do.

zene -5 carboxylic gagid-f-phenyl-anile. l-amino-Z-inethylben- 1-(2-hydroxydiphenyl- Brown.

zene -5- carboxylic ene oxide-acarboylacid-4-phenylamino)-2-methoxyanilide. benzene. l-amino-Z-ethoxtbeny xy p y rey brown- 'zene -5- carboxylic ene; ox1de-3-carboylaci d-4-pheny1- am1no)-2:5-dimethanilide. wry-benzene V l-amino-Z-methoxyl-(2-hydroxydiphenyl- D0.

benzene-Maybcxylic eneox1de-3'-carboylacid -4' -pheny1 amino)-2:5-dimethanilide. oxy 4 chlorobenzene. Do 1-(2'-hydr0xydiphenyl- Reddish grey.

- en eox1de-3-carboylamino)-2-methoxybenzene.

Do 1-(3-hydroxyd1phenyl- Blue grey.

enesulphide-2'-earboylamino)-2-ethylbenzene.

Do l-(3-hydroxydiphenyl- Do.

enesulphide-2'-carboylamino)-2- methyl-i-methoxybenzene.

Do 1-(8'-hydroxydiphenyl- Do.

enesulphide-2-carboylamino) 2:5-

- dimethoxyi-chloro benzene.

Do 1-(3-hydroxydiphenyl- Do.

enesulphide-2'-carboylamino) benzene.

eral formula in which X indicates a substituent of the group consisting of alkyl, alkoxy and halogen; Y indicates a radical of the group consisting of carbazol, diphenylenoxide and diphenylensulfide wherein the hydroxy group and the azo group are in orthoposition to each other; R, indicates an aryl radical of the group consisting of phenyl and naphthyl; vZ1, Z: and Z3 each indicates a member of the group consisting of H, alkyl, alkoxy, halogen.

.2. {the monoazgdyeetqffs of the follow ing. .gen-

in which X indicates a substituent-o'f "the group consisting of alkyl, alkoxy and halogen; :R indicates an aryl radical of thegroup consisting of phenyl and naphthyl; Z1, Z2 and Z: each indicates a member of the group eonsisting'of H, 'alkyl, alkoxy and halogen.

3. The monoazodye'stufis, of the following general formfila in which X indicates asubstituent of the group consisting of methyl and 'rne'thoxy and Z indicates a substijsuent of.the group consisting of Cl, Br and methyl.

1Themonoazodyestiifpf n-othe following iotmula '1 oom Ocl 5. The monoazodyestuff of the following formula ERNST FISCHER.

References Cited in the file of this patent UNITED STATESPATENTS Number Number Name Date Fischer; June 18, 1940 Fischer Nov. 26, 1940 FOREIGN PATENTS Country Date r Germany ,N 2v.- 10, 1943 

4. THE MONOAZODYESTUFF OF THE FOLLOWING FORMULA 